19.

Interstellar Chemistry
1. Introduction to Interstellar Chemistry
2. Chemical Processes & Models
3. Formation & Destruction of H2
4. Formation & Destruction of CO
References
Duley & Williams, "Interstellar Chemistry" (Academic 1984)
van Dishoeck, UCB Lectures Notes (2000)
Genzel, Sec. 3 of "Physics & Chemistry of Molecular Clouds"
in "Galactic & Interstellar Medium" (Springer 1992)
van Dishoeck & Blake, ARAA, 36, 317, 1998
van Dishoeck, ARAA, 42 119 2004
Data Collections
V. Anicich, ApJS 84, 245, 1993
www.rate99.co.uk
http://kinetics.nist.gov/index.php

1. Introduction to Interstellar Chemistry

Astrochemistry deals with the formation and destruction
of multi-atomic systems of interest to astronomy and
planetary science, including stellar and planetary
atmospheres and comets. The systems of interest range
from diatomic molecules like H2 and CO through large
molecules like PAHS, dust grains and even larger bodies.
We focus on the new field of interstellar chemistry whose
growth was stimulated by the discovery of molecules in the
ISM and which also encompasses nano-through micronsized particles. Two basic differences between interstellar
chemistry and terrestrial chemistry are:
1. Much lower pressures
2. Extreme temperatures from cryogenic to ultra-hot
3. External energy sources, e.g., far-UV, CRs, etc.

Special Features of Interstellar Chemistry

Cosmic Rays

Dynamical Changes

UV Photons

Cosmic Mix of Elements

n,T,x

Each gas element is an open system subject to

external effects.
The low ISM pressure means that the main phases are
gas and solid, bridged by large molecules & solids.
The chemistry is heterogeneous, with reaction between
gas and solid, especially in the surface layers of solids.
The chemistry is often time-dependent, i.e., chemical
timescales may be long compared to thermal & dynamical.

The Importance of Interstellar Chemistry

More than 140 molecules have been detected
(not counting isotopic variants).
Examination of the list (next page) suggests some
generalizations: Small chains favored over rings.
Many unsaturated radicals (20%) and ions (10%).
Some astrophysical objectives of interstellar chemistry:
(1) Model chemical observations in terms of
temperature, density, & ionization fraction
(2) Find diagnostics for total elemental abundances
and total hydrogen density, e.g., relate measurements
of OI to the total abundance of oxygen or CO to H2..
More generally, find diagnostics of the physical
parameters.

The Interstellar Molecules

Types of Chemical Models

Shielded dense cloud
Partially transparent diffuse clouds
Photon-dominated regions
Collapsing clouds
Shocks
Stellar winds
Cloud cores & YSO envelopes
Disks
Modeling interstellar chemistry became intense after 1973. much of it
Influenced by Salpeter & Co. (e.g., Gould, Werner, Watson, & Draine).
Other pioneering work emphasizing grain catalysis was by Bates &
Spitzer (ApJ 113 441 1951) & Stecher & Williams (ApJ 146 88 1966).

Most chemical modeling after 1973 starts with gas-phase

chemistry and later attempts to include surface interactions.

2. Gas Phase Chemistry

We begin with gas-phase chemistry for cool (T < 100 K)
low-ionization (xe < 10-3) gas with minimal attention to
surface chemistry and primary application to:
Diffuse Clouds and Exteriors of Molecular Clouds
Moderate density - typically 100 cm-3
Low temperature - typically 50 K
Low ionization - mainly H+ and C+
Molecular Cloud Interiors
Intermediate density - typically 500 cm-3
Low temperature - typically 20 K
Very low ionization - typically 10-7
NB: all clouds are inhomogeneous.

Chemical Activity
Most chemical reactions do not proceed under the above
conditions, e.g., the most abundant molecules in cool
dense clouds, H2 and CO, do not react on collision.
Even exothermic reactions may not proceed unless the
kinetic energy is larger than some characteristic
activation energy of order 1 eV.
To activate cold chemistry, energy has to be provided
externally in the form of UV photons, cosmic rays, or
mechanical energy.
Energizing the chemistry is particularly important in
partially unshielded regions where UV photons photodissociate molecules at the rate 10-10s-1 (on a timescale as short as 300 yr)

Generic Reaction Types

1. One-body
h + AB A + B :

at a volumetric rate G (AB)n(AB)

CR + AB AB+ + e : at a volumetric rate (AB)n(AB)

2. Two-body
A + B C + D at rate per unit volume

k (A, B; T )n(A)n(B) = k (A, B; T ) x(A) x(B)nH

The rate coefficient is often a function of T, as in reactions

with activation energy, where it is proportional to exp(-Ta/T).
Conclusion: Reaction rates are sensitive to both T and nH.
NB Three-body reactions are rare because of the low
density of the ISM.

Examples of Specific Reactions

Many of these are able to overcome the weakness of ordinary
chemical reactions in cool regions
Neutral Radical Warm regions (> 300 K); k up to 10-10 cm3 s-1.
O + H2 OH + H
OH + H2 H2O + H
O + OH OH2 + O
Ion-Molecule Important for cool regions; often k ~10-9 cm3 s-1 in
the absence of activation energy (most very exothermic reactions)
charge exchange
H+ + O O+ + H
(H) abstraction
O+ + H2 OH+ + H
proton transfer
H3+ + O OH+ + H2
Radiative Association - Weak, but may sometimes be the only
pathway, e.g., in the dark ages
e + H H- + h

H + H+ H2 + + h

Photodissociation Almost always important; typical ISM rate

~10-10 s-1.
hv + H2 2H
hv + OH O + H

(via Lyman and Werner band lines)

N.B. Many cross sections have not been measured accurately

Dissociative Recombination - Always important; k~10-7 cm3 s-1
e + H3+ 3H, H2 + H (branching 3:1)
e + H3O+ OH + H2, OH + 2H, H2 O + O
Addendum on Surface Reactions Important but poorly understood,
e.g.,
H + H(Gr) H2 + Gr (geometric rate; e.g., Hollenbach & Salpeter 1971)
Additional processes: adsorption & desorption; catalysis; icing!

3. Formation and Destruction of H2

A. Formation in Cool regions (T < 100-200 K)

The simplest process, radiative association of two H atoms,

H + H H2 + h,
is very weak (a ro-vibrational, quadrupole transition). For more than 40
years it has been generally assumed that H2 is formed on grains, as in
volumetric formation rate = R nH n(H)
where, following Hollenbach & Salpeter (1971), R is essentially the rate
at which H atoms strike the available grain surface area (per unit
volume) with a sticking factor of 1/3,
R = 3 X 10-17 cm3 s-1(T/100K)1/2.
Recent laboratory experiments by Vidali et al. raise questions on how
the recombination actually occurs and lead to a rate coefficient
that is significantly smaller (e.g., Lipshat et al. MNRAS 348 1055 2004).

Formation of H2 (contd)
B. Formation in Warm Regions ( T > 300 K ) radiative association
of H ions of both signs
1.

H+ + H H2+ + hv
H2+ + H H2 + H+

2. e + H H- + hv
H- + H H2 + e

Typical applications are post-recombination and outflows from YSOs.

C. Formation in Very Dense Regions ( > 1012 cm3 s-1) - three-body
reactions. e.g.,
3H H2 + H

2H + H2 2H2

with rate coefficients 10-32 10-33 cm6 s-1. Typical applications

are cool stellar atmospheres, YSO disks and jets.

Photodissociation of H2
As discussed in Lecture 18, H2 is dissociated in a two-step process
when a far UV photon is absorbed in a Lyman or Werner transition
below 1108 , and the excited molecule decays into the continuum
of the ground electronic state with the emission of a photon in the
1300-1700 band.
With typical oscillator strengths of 0.03, the L-W lines easily become
optically thick. For example, with a Doppler parameter b = 3 km s-1,
the standard formula for optical depth at line center

(0) = f lu

e 2

Nl

me c

yields N(H2) > 1014 cm-2. Thus absorption occurs mainly in the
damping wings of the Lyman and Werner lines. The theory of H2
photodissociation was developed by collaborators & students of
Salpeter, e.g., Hollenbach, Werner, & Salpeter (ApJ,163, 166,
1971), and applied to the early Copernicus observations by Jura
(ApJ 191 375 1974) and Federman, Glassgold & Kwan
(ApJ, 227, 466, 1979; FGH)

Photodissociation of H2 (contd)
FGH showed that, in the presence of H2 absorbers, the transmitted
dissociating radiation is given by the derivative of the equivalent width.
The simple proof follows by considering the definition of equivalent
width (e.g., Lecture 2) for the transition j k:

W jk = d ( ) 1 exp( N j s jk ( ))

Here jk()=sjk () is the frequency dependent absorption

cross section. Differentiation leads to:

W jk

( N j s jk )

dv s

jk

= dv ( ) exp( Njsjk ( ))

( ) exp( N j s jk ( ))

dv ( )s

jk

( ))

This ratio is called the line self-shielding function Jjk

W jk
( N j s jk )

==

dv s

jk

( ) exp( N j s jk ( ))
J jk

dv ( )s

jk

( ))

It gives the absorption cross section, averaged over the line

shape, taking into account the attenuation of the dissociating
radiation by H2 itself; it can be considered a function of the
optical depth at line center

(0) = N j s jk (0) = f jk

e 2

Nl

me c

(for Doppler broadening)

Jjk is a decreasing function of optical depth (or column),

starting from unity at zero optical depth. Having already
analyzed the dependence of W on optical depth, FGK
obtain the dependence of Jjk by differentiation.

Behavior of the Curve of Growth

& Line Self-Shielding Function
There are three regimes of equivalent width, depending on
optical depth at line center:
0 << 1
linear
~ 0
0 > 1
flat or logarithmic ~ log0 1/2
0 >> 1
square-root
~ 01/2
Differentiating W gives the corresponding behavior for J:

0 << 1

0 > 1
0 >> 1

J=1
J ~ 1/0
J ~ 0-1/2

In practice, the Lyman & Werner bands are usually optically

thick, and the dissociation rate decreases as the inverse
square root of the H2 column density

Abundance of H2 in Diffuse Clouds

(and The Edges of Thick Clouds)
Follow FGK (or Warin et al. A&A 308 535 1996 for a more detailed
theory). Balance the photodestruction rate G0Jn(H2) against the grain
formation rate RnHn(H) while satisfying mass conservation, nH=n(H) +
2n(H2). The photo rate is calculated summing all accessible Lyman &
Werner band transitions. The effects of other absorbers of 912-1108
radiation are also easy to include.

x(H 2 ) =

1
1+

G0 J
2nH R

M
N (H 2 )

M = 6.75 1011 cm -2 , R = 3 10 17 cm 3 s -1 (T / 100K )1/ 2 , G0 = 6 10 11 s 1

is the ratio of the formation to the photodissociation time scales.
Grain formation is a slow process, e.g., the formation time at 100 K is
-3

100cm
1

= 10 Myr
RnH
nH

Spatial Variation of the H-H2 Transition

N(H2)

dashed curve: Glassgold & Langer

(ApJ 193 73 1973, similar to HWS)
a. refined FGK theory (ground state)
b. with dust
c. thermal level population
d. collisional-radiative population
dotted-curve: 10% conversion

NH
dots - Copernicus data
line - FGK theory

Limited observational support for the

theory of H2 formation & destruction

4. Formation and Destruction of CO

A. Formation in Cool Regions: Fast ion-molecule reactions
k ~10-9 cm3 s-1
O+ + H2 OH+ + H
OH+ + H2 OH2+ + H
OH2+ + H2 OH3+ + H

or

H3+ + O OH+ + H2
H3+ + OH OH2+ + H2
H3+ + H2O OH3+ + H2

and fast dissociative recombination, ~10-9 cm3 s-1 :

OH+ + e O + H
OH2+ + e OH + H and O + H2 or 2H
22% OH
OH3+ + e H2O + H and OH + H2 or 2H, etc. 75% OH
OH is a crucial intermediary in the formation of CO, and it requires
H2 as a precursor. But the synthesis of OH is driven by the ions
O+ and H3+ (to be discussed in Lecture 20). This scheme also produces
H2O and other O-bearing molecules, as will also be discussed.

Gas-Phase Synthesis of CO
The efficiency of ion-molecule synthesis of OH depends on the ratio of
reaction rates representing the competition between formation and
destruction, k x(H2)/ x(e). In diffuse clouds with x(e) ~10-4 and x(H2) >
0.01, this ratio is ~ 1.
CO is rapidly produced from OH by fast reactions, e.g.,
C+ + OH
CO+ + H2
C + + H 2O
HCO+ + e

CO+ + H
HCO+ + H
HCO+ + H
CO + H

or, where C is more abundant

than C+, the neutral reaction
is fast: C + OH CO + H

The idea of using ion-molecule reactions to initiate low-temperature

interstellar chemistry is due to WD Watson (ApJ 183 L17 1973) and Herbst
& Klemperer (ApJ 185 505 1973), although the latter did not give the correct
theory for the synthesis of CO. Klemperer was responsible for the
identification of an unknown mm transition with HCO+ (ApJ 188 255 1974).

Cosmic Rays and the Synthesis of OH and CO

Where do the ions required by ion-molecule chemistry come from?
In cool regions, the usual answer is cosmic rays. In Lecture 14, we
estimated the cosmic ray ionization rate on the basis of demodulated
satellite observations out to 42 solar radii as

CR (> 2 MeV) 5 10 17 s 1
This refers to the ionization of atomic H, i.e,
CR + H H+ + e
Similar rates applies to CR ionization of He and H2,
CR + He He+ + e
CR + H2 H2+ + e and H+ + H (5%)
But H2+ is very reactive:
H 2+ + H H + + H 2
H 2+ + H 2 H 3+ + H 2
and leads to H3+, the pivotal ion in the ion-molecule chemistry.

Formation and Destruction of CO (contd)

B. Formation in Warm Regions - Radical reactions:
O + H2 --> OH + H
C + OH --> CO + H

(slow)
(moderately fast)

Destruction of CO
1. In partially UV-shielded regions, the same two-step process operates
as for H2, with the following changes:
a. G0 = 2x10-10 s-1 (for the mean UV radiation field),
b. self-shielding is reduced since usually x(CO) << x(H2).
c. mutual shielding in the 912-1108 band by H2 and even
some lines of atomic H are importnat
d. mutual shielding of the isotopes 13C and C17O by the lines
of 12CO and H2 occurs
2. In well-shielded (thick) clouds, CO is destroyed by the fast ionmolecule reaction
He+ + CO C+ + O + He.

Synthesis of CO: Summary

All of the ion-molecule reactions for CO are fast, but the
ions may be in short supply in dense shielded regions
because their abundances depend on CR/nH.
In partially shielded regions the time scales are short,
but only a small fraction of carbon goes into CO because
of strong photodissociation.
Slow formation of H2 may be the limiting factor in the
synthesis of CO in atomic regions.
Much depends on the initial conditions and whether
steady state can be reached..